Azo dyestuff from 2-3-hydroxynaphthoic acid arylids and process of making the same



Patented Jan. 21, 1930 UNITED- STATES PATENT OFFICE LEOPOLD LASKA ANDARTHUR ZITSCHER, OF OFFENIBACHON-THE-MAIN, ASSIGNORS TO GENERAL ANILINEWORKS, INC., 01 NEW YORK, N, ,Y A CORPORA- TION OF DELAWARE AZODYES'I'UFF FROM 2 3-HYDROXYNAIPHTHOIC ACID ARYLIDs AND PROCESS OF MAKING'HE SAME I No Drawing. Application filed May 24, 1926, Serial No.111,370, and in Germany May 28, 1925.

The present invention relates to new azo dyestuffs from2-3-hydroxynaphthoic acid arylids and processes of making the same.

We have found that exceedingly valuable novel azo dyestufis are obtainedif 2-3-hydroxynaphthoic acid'arylids are allowed to couple with thediazo compounds obtained from amines of the general type wherein Yrepresents a non-reactive substituent such as alkyl, oxyalkyl, oxyarylor halogen; X represents either the sulfone group S0 or the carbonylgroup CO and R represents alkyl, aryl, aralkyl or the grouping- Ifbis-2-3-hydroxynaphthoyl-arylendiamines of the general formula are usedas coupling compounds, these will react either with 2 molecularproportions of a monoamine of the type in which formula the letters Xand have the 45 same meaning as defined above.

Themost probable graphical representation for our novel dyestuffs is theformula These coloring matters are in the dry state reddish to darkcolored powders, which dissolve in concentrated sulfuric acidwith fromblue to dark violet colors. By reduction the original amines of the typeare recovered together with 1-amin0-2-3-hydroxynaphthoic acid arylids.The new dyestufls maybe produced eitheras such or-on a base which may beeither a substratum or the vegetable fibre.

Mixed with or precipitated on substrata these novel dyestufl's producevaluable and fast color lakes. They are furthermore of great interest inthe dyein of vegetable fibres. The dyestufi is in this case directlyproduced on the fibre, the dyeings obtained are of-exceeding y clearshades andparticur larly fast to kier boiling.

Some of the amines which can be used in our novel process are forinstance the following: 2-aminotolyll-phenylsulfone3-aminol-phenoxybenzophenone 3-3-diamino 4 4-dimethoxy diphenylsulfoneNH; NH!

l mooGsm-O-o cm 2-aminotolyll-benzylsulfone2-amino-1-methoizyl-phenylsulfone NH: I

and the 2-3-hydroxynaphthoic acid arylids useful in our novel processcan be exemplified by the following:2-3-hydroxynaphthoyl-1-2-phenetidine \OCH \0 2 i 2-3-hydroxynaphthoicacid-beta-naphthalid:

mwoma'w 2 -3-hydroxynaphthoio acid-alpha naphthalid ,6]; @CO-NH82-3hydroxynaphthoic acid-m-chloranilid:

The following examples will further illustrate our novel process and theproducts obtained by it. We wish it however to be understood that we arenot limited to the particular conditions nor to the specific'productsmentioned therein. The parts are by weight.

Example 1: 8.3 parts Q-amino-l-methoxy- 4-phenylsulfone are thoroughlystirred up with 16 parts hydrochloric acid (spec. grav.

1.160) 50 arts water and ice added, and then diazotize with a solutionof 2.1 parts sodium nitrite in 15 parts water. To this diazo a filteredsolution of 9.2 parts 2-3-hydroxynaphthoyl-1-2-phenetidine in 8.4 partscaustic soda (36 B.), 1 part Turkey-red oil; 3.67 parts crystal sodiumacetate in 150 parts water is run in. The coupling is finished afterseveral hours stirring. The dyestufi is so obtained in form of abrilliant red paste, mixed with the usual substrates it forms a fieryred lake. After drying it dissolves in concentrated sulfuric acid with abluish-violet color and has most probably the formula:

HaC O\ N=N r 0 (IO-NHO Example 3 Well boiled out and dried yarn ispadded with a solution containing per liter 7 gr. 2-3-hydroxynaphthoicacid-alpha-naphthalid, 14; cc. caustic soda 34 B. and 8 cc.

. Turkey-red oil, it is then well wrung and without drying developedwith a solution containing per liter the diazo obtained from 4.9 gr.2-amino-tolyl-4-phenylsulfone and which was neutralized with calciumcarbonate. After rinsing, soaping and drying the am is dyed a bluish-redshade of very goo fastness to kier boiling.

The dyestuff precipitated on the fibre has most probably the formula:

oxy-diphenylsulfone which has been made organic acid by the addition ofsodium ace- H,c tate. After rinsing, soaping and drying the cotton 1sdyed a claret shade of very good sol-O fastness to her bolhng. Thedyestufi' pre- N=N clpltated on the fibre has most probably the onformula:

HscoOsozO-ocm oo-NH N=N \N=NL /OH no If in this example the diazo from5.8 gr. 3-am1no-4-phenonybenzophenone 1s substl- \O 0/ tuted for thedlazo from Q-ammo-tolyllphenylsulfone a very fast wme red shade oncotton yarn 1s obtamed.

Example 4: Cotton materlal prepared 1n C1 the usual way Is padded wlth asolutlon containmg per hter 10 gr. 2-3-hydroxynaphtho1c The $511116Shades d P P I S I acid-m-chloranilid, 15 cc. caustlc soda 34B, areObtalned y P g the dyestuffs and 8 cc. Turkey-red 011,1t 1s then Wellwrung the fibre by the usual prmtmg processes, and Without dryingdeveloped w1th a solutlon The followmg table glves the shadesobcontaining per llter the diazo compound 0btamed on cotton matenal byusing other of tained from 6.2 gr. 3-3 d1am1no-4-4'-d1methour novel azoc0mb1nat1ons:

Diazocompound of Combined with 2.3-hydroxynaphthoylsh d2-amlilno-tolyl-4-ethyl-sullone of the for-- 5-chl0ro-2-anisidiue of theformula: Fierg yellowish III. 8: re

NH: v 0011;

onr-O-sokclm 1 oo-NH l v l 2-ammo-toly1-4-benzyl-su1fone of the formula:

Yellowlshscarlet CHa-QSOwCHg-O Aniline d 0. A 5-eh1oro-2-toluidineBlulsh red D0. 3-nitraniline Scarlet 5 Do fl-naphthylamine Clear scarletred 3-amino-4-chloro-diphenylsulfone of the formula:

H: (JP-OSOg-O fl-naphthylamine Red Do. 3-nitraniline Yellowish red Do.3-toluidine Orange red Do. Z-phenetidine Orange redz-amino-phenetol-a-phenylsulfone of the formula: I

NH! I 0,1150 so,- 5-chloro-2-toluidine Blulsh red Do. Z-anlsidine Winered D0, 5-chloro-2-anisidine Scarlet red Do. 2-phenetidine Clear red2-amino-tolyl-4-phenylsultone of the formula:

. Frery yellowlsh CH 802-- 4-tolu1du1e red D0. 7 2-anisidine Fieryscarlet Do. 4-chl0ro-2-an1sidine Red Do.Bls-2.3-hydroxynaphthoyl-dianisidineofthe formula: Bro n mm gar- 12 (Twomolecular proportions) net 4 on -..c0-NHOO-NHO o l Q \OCH;

Diazocompound of Combined with 2.3-hydroxynaphthoyl Shades3-amino-4-methoxy-aceto-phenone o! the 2.3-hydroxynaphthoyl- I formula:NH

OH| OOCH; -chloro-2-tolu1dine 4 Claret red 13-alnlno-4-methoxy-benzophenone of the formula:

omo-O-oo-O 4-hloroaniline Claret red Do. fi-chol oro-2-anisidine Claretred 3-amino-4-phenoxy-bcnzo-phenone oi the formul NH: 7 15 ifi-naphthylamine Claret red 3.3giamino-4A ditolylketone of the ior- (Twomolecular proportions) NH: .NH, I v

CH; OO CH; Aniline Fiery scarlet Do. fi-naphthylamine Fiery scarlet Do.4-toluidine Fiery scarlet Do. 4-chloroaniline Clear scarlet red D03-P11el1etidim Clear scarlet red We claim: and R represents eitheralkyl, aryl, aralkyl 1. In processes of producmg azo dyestufi's or thegrouping: from 2-3-hydroxy-naphtho1c ac1daryl1ds the steps comprisingdlazotlzmg an amine of the Y 0 general type:

N=N NH: I

1 H0 12-): Y I a Aryl-NH-CO V 35 wherein Y represents alkyl, oxyalkyl,oxym aryl or halogen; X represents either the sul- Whlch are 111 the ystate leddlsh dark fone group S0 th carb yl group 00 coloredpowders,soluble 1n concentrated suland R reprgsents lkyl, l, lk or th func ac1dwith from blue to dark violet colors, in grouping; 21nd which byreduction yield an amine of the and coupling the diazotized compound soobtained with a 2-3hydroxynaphth0ica id 1n whlch X and Y, have the sameslgnlficance arylid. as above and R represents elther alkyl, aryl,

2. As new products azo dyestuffs having aralkyl 1' he grouplngt mostprobably the general formula: Y

: and a l-amino-2-3-hydroxynaphthoic acid 5 ar lid, and which whenproduced on vege- HO.- ta 1e fibres yield reddish-shades of excellentfastness'to kier boiling. 3. Vegetable fibres dyed with the dyestufis 60wherein Y stands for alkyl, oxyalkyl, oxyde cri ed in claim 2- 105 varyl or halogen; X represents either the sul- 4. In p ocesses ofproducmg azo dyestufiz's fone group SO or the carbonyl group CO, from2-3- ydroxynaphthoic acid arylids the Aryl-NH-C O steps comprisingdiazotizing an amine of the general type:

wherein Y stands for alkyl, oxyalkyl, oxyaryl, or halogen; X representseither the sulfone group SO or the carbonyl group GO, and R representsalkyl, aryl or aralkyl, and coupling the diazo compound obtained with va 2-3-hydroxynaphthoic acid arylid.

' from blue to dark violet colors and which by 5. As new products azodyestufis having most probably the general'formula:

Aryl-NH-CO wherein Y represents alkyl, oxyalkyl, oxyaryl or halo en; Xrepresents either the sulfone group or the carbonyl group CO, and Rrepresents alkyl, aryl or aralkyl, which are in the dry state reddish todark colored powaryl, or halogen and R represents alkyl, aryl oraralkyl, which dyestuffs are in the dry state reddish to dark coloredpowders soluble in concentrated sulfuric acid with from blue to darkviolet colors and which by reduction yield an amine of the type:

wherein Y and B have the same significance as above and a1-amin0-2-3-hydroxynaphthoic acid arylid, and which when produced onVegetable fibres yield reddish shades of excellent fastness to kierboiling.

9. Vegetable fibres dyed with the dyestufi's described in claim 8.

In testimony whereof we have hereunto set our hands.

LEOPOLD LASKA. ARTHUR ZITSCHER.

derssoluble in concentrated sulfuric acid with Y 7 reduction yield anamine of the type:

HGY

in'which X, R and have the same significance as above and a1amino-2-3-hydroxynaphthoic acid arylid, and which when produced onvegetable fibres yield reddish shades of excellent fastness to kierboiling.

6. Vegetable fibres dyed with the dyestuffs described in claim 5.

7. In processes of producingazo dyestuffs from 2-3-hydroxynaphthoic acidarylids the steps comprising diazotizing an amine of the general type:

R-SOaGY R-smO' Y Nfl- - Aryl-NBf-C wherein Y stands for alkyl, oxyalkyl,oxy-

